Process for desulfurizing and isomerizing light normal paraffins



N. L. CARR 2,951,888

PROCESS FOR DESULFURIZING' AND ISOMER'IZING LIGHT NORMAL PARAF'F'INS Sept. 6, 1960 Filed April 29, 195s INVENTOR.

NORMAN L. CARR BY ATTORN Y United States PROCESS FOR DESULFURIZING AND ISOMER- IZING LIGHT NORMAL PARAFFINS Norman L. Carr, Crystal Lake, Ill., assignor to The Pure Oil Company, Chicago, Ill., a corporation of Ohio Filed Apr. 29, 1958, Ser. No. 731,778

9 Claims. (Cl. 260-683.65)

K hydrogen and an isomerization catalyst under isomerizing conditions. More particularly, the process is concerned with a preliminary treatment of the normal paraffin hydrocarbon feed which mitigates and in most cases completely avoids the drastic decrease in catalyst activity with time which is often encountered in isomerization processes.

Branched-chain isomers of Cri-C7 normal saturated paratin hydrocarbons are particularly valuable for use in upgrading gasolines to increase their octane numbers for use in high compression gasoline engines. It is therefore highly desirable to have a convenient and effective process for isomerization of normal CVC, hydrocarbons.

Processes have previously been developed to isomerize individual normal parain hydrocarbon and mixturesl of normal parain hydrocarbons of the C4-Cq range by vapor phase contact with various isomerizing catalysts. Catalysts which have been used include platinum on alumina, nickel on silica-alumina, nickel-molybdenum on silica-alumina, and palladium on silica-alumina. These catalysts lare not the equivalent of each other for all purposes since the variations in conditions required for isomerizing low-moleculaI-weight parain hydrocarbons vary considerably for these and other isomerization catalysts. Some of the catalysts have also been used under different processing conditions of temperature, pressure, etc., in the reforming of gasoline to increase the aromatic content thereof. It has beenfound, however, that conditions which are satisfactory for catalytic reforming are not satisfactory for isomerization of pure low-molecularweight paraiiins, or mixtures thereof, or feed stocks which are predominantly parainic.

It is, therefore, an object of this invention to provide a new and improved process for the isomerization of hydrocarbon feeds which consist of one or more saturated normal paraiiin hydrocarbons of the Cac-C7 range.

A further object of this invention is to isomerize CFC, normal paraiiin hydrocarbons in the presence of free hydrogen at elevated temperatures and pressures over a suitable isomerization catalyst supported on an acidic silica-alumina support.

Another object of this invention is to provide an improved catalytic isomerization process in which the decline of catalyst activity is effectively mitigated.

A feature of this invention is the provision of an improved isomerization process using an isomerization catalyst consisting of nickel, nickel-molybdenum, or palladium on an acidic silica-alumina support in which the hydrocarbon feed has a sulfur content of less than 1 p.p.m. (part per million), thereby mitigating the decline in catalyst activity with time.

Another feature of this invention is the provision of arent i() F Patented sept. e, raso an improved isomerization process in which a hydrocarbon feed consisting of one or more normal saturated parain hydrocarbons of the C4-C7 range is desulfurized to acontent of less than 1 p.p.m., and the desulfurized feed isisomerized by contact with a metal isomerization catalyst supported on an acidic silica-alumina support, in the presence of free hydrogen at elevated temperatures and pressures.

Other objects and features of this invention will become apparent from time to time throughout the specification and claims as hereinafter related.

In the accompanying drawings, to be taken as part of this specification, there are illustrated certain aspects of this invention, in which drawings:

Fig. 1 is a flow diagram of a preferred embodiment of this invention illustrating the desulfurization of a normal paratiin hydrocarbon feed followed by introduction of the desulfurized feed into a catalytic isomerization reactor for conversion of normal parains to isoparains, and

Fig. 2 is a graph showing the change in catalyst activity of a palladium-on-silica-alumina catalyst for n-pentane feed containing varying amounts of sulfur therein.

This invention consists essentially of a process for the isomerization of CFC-1 saturated normal paratn hydrocarbons. The hydrocarbons treated in this process may be relatively pure hydrocarbons, or mixtures of one or more of said hydrocarbons, or a hydrocarbon fraction or cut which is predominantly a mixture of normal (L-C7 saturated paraffin hydrocarbons. The hydrocarbon feed is first subjected to a desulfurization process, such as catalytic hydrodesulfurization, including causticand water-washing and drying of the eflluent, or stabilization, to reduce the sulfur content to the range of about 5-50 p.p.m. This hydrocarbon feed is heated to an elevated temperature, preferably about 40G-800 F. (although higher temperatures may be used), and passed through a desulfurization reactor or guard case containing a suitable desulfurizing reactant to x and remove sulfur without the formation of hydrogenV sulfide. Desulfurizing catalysts which are well known in the prior art for removing sulfur (as hydrogen sulde) from hydrocarbons include various metals such as copper, nickel, iron, molybdenum and cobalt, and their oxides and various compounds thereof, such as copper molybdate, cobalt molybdate, nickel molybdate, etc., preferably supported on a silica, silica-alumina, or alumina support. Such materials are also effective as reactants in a guard-case to fix and remove sulfur Without the formation of hydrogen sulfide. The desulfurization catalyst and reactant may be the same as the catalyst used in the isomerization reaction. Fixation of the last sulfur from the hydrocarbon stream is accomplished by the action of the guardcase material as a reactant for sulfur compounds, and the sulfur-containing products therefrom are held within the guard case. This chemical treatment usually reduces the sulfur content of the feed to less than about l p.p.m. and may produce a sulfur content of practically zero. The completely desulfurized hydrocarbon feed is then passed to the isomerization reactor, at a temperature of 650800 F., with free hydrogen at a. total pressure in the range of 10D-1000 p.s.i.g. The isomerization reactor contains a catalyst such as nickel, nickel-molybdenum (reduced nickel molybdate), or palladium, supported on an acidic silica-alumina (S0-90% silica) support. It is to be noted that these catalysts are not considered equivalent for all purposes and are considered together here only because of their common sensitivity to trace amounts of sulfur under .isomerization reaction conditions. The product from the catalytic isomerization reactor contains a high proportion of isoparaflins. By thoroughly desulfurizing the hydrocarbon feed stock before introducing the same to the isomerization reactor, it is possible to on a 75% silica-25% carry out the isomerization reaction for extended periods of time without loss in catalyst activity. Some of these catalysts, when used under high-temperature reforming conditions, Will tolerate a sulfur concentration of 30-50 p.p.m. in the hydrocarbon feed Without decline in catalyst activity. In fact, platinum on alumina is sometimes used under reforming conditions-with hydrocarbon feeds having added sulfur. In the design of an isomerization plant using a palladium on silica-alumina catalyst, a reduction of the sulfur content of the feed from 13 ppm. to less than 1 p.p.m. will permit a 50% reduction in the reaction size. This eifect of removing substantially all of the sulfur, to a concentration less than -1 ppm., in this isomerization process was ycompletely unexpected from the prior art disclosures.

EXAMPLE I Referring now to Fig. ;l of the drawings, there is shown a flow diagram for the process .of my invention. Technical grade n-pentane, containing more than 20 p.p.m. of sulfur, is introduced into a ,catalytic desulfurization unit along with a suitable supply of hydrogen (at a mol ratio of hydrogen to hydrocarbon of 1.5 to 3.0) and subjected to conventional catalytic hydrodesulfurization conditions to remove the major proportion of sulfur. The hydrocarbon effluent from the catalytic desulfurization unit may have a sulfur content of less than about .2 p.p.m. If it is less than about 1 p.p.m., no further desulfurization treatment is necessary. If not, the catalytically desulfurized pentane ows through a guardcase containing nickel molybdate before entering the isomerization reactor, for removal .of substantially all of the remaining sulfur from the feed. The guard case or supplemental desulfurization unit is provided with a reactant consisting of 15% reduced nickel molybdate on a 75% silica-25% alumina support, which reactant is capable of reducing the sulfur content of the pentane practically to zero, to a value substantially less than 1 p.p.m. The desulfurized pentane feed then passes to a catalytic isomerization reactor. The reactor contains a catalyst, consisting of nickel molybdate on 75% ,silica-,25% alumina acidic catalyst support, which has been activated by a conventional oxidation-reduction cyclic technique. The reaction in the isomer-ization reactor is carried out under a pressure of 500 p.s.i.g., at 700-710" F. using a hydrogen/pentane mol ratio of 2.0 and a pentane liquid volume hourlyspace Velocity of 1.5. Under these reaction conditions, Vthe effluent hydrocarbons from the isomerization reactor contained `42% isopentane and 45% n-pentane, which represented a yield per pass of 41%, a conversion selectivity of 77%. This run was continued for a period of 6 hours during which time the yield of isopentane actually increased slightly with time.

EXAMPLE II In another experiment, technical-grade pentant having an initial sulfur content of 22 p.p.m. was hydrodesulfurized, caustic-washed, Water-washed and dried to reduce the sulfur content to less than 10 ppm. The catalytically desulfurized pentane was then passed through a second desulfurizer unit, containing a 10% reduced nickel molybdate on a 75/25 silica-alumina support, at a temperature of 550 F. yand pressure slightly over 500 p.s.i.g. The pentane was fed at a liquid volume hourly space velocity of 3.0 together with water vapor at a partial pressure of mm. Hg, and hydrogen in a hydrogen pentane ratio of 1.2. The sulfur content of the pentane was reduced in the second -desulfurization step to substantially less than l p.p.m. The completely desulfurized pentane was then heated and passed into a catalytic isomerization reactor where it Was contact with a catalyst consisting of 10% reduced nickel molybdate supported alumina acidic catalyst, as carrier, The reaction was carried out in the isomerization reactor per pass of 53%, and

at a pressure of about 500 p.s.i.g., and temperature of 700 F. The product from the reactor contained about 32% isopentane constituting a yield of about 31%, a conversion of 36%, and selectivity of 87%. 'Ihis run was carried out for a period of 6 hours during which time the isopentane yield actually increased slightly with time.

EXAMPLE III Another experiment was carried out following the procedure of Examples I and II using nickel molybdate on silica-aluminaas reactant in the second desulfurization step 5, anda catalyst-consisting of 3% nickel metal on 75 silica-25% alumina, asV catalyst support, in the isomerization reactor. The pressure in the second desulfurization unit `and theisomerization reactor was maintained at about 500 p.s.i.g. The second desulfurizer unit was maintained at a temperature of 550 F. While the isomerization reactor was maintained at `740-750" F. Pentane feed and hydrogen were charged at a hydrogen/Pentane mol ratio of 1.0, a liquid volume hourly space velocityV of 3.0. The feed contained a small amount of water vapor at a partial pressure of 10-15 mm. Hg. Isopentane yield in the effluent from the isomerization reactor remained constant for a period of 17 hours at which time the testwas terminated. This run produced an isopentane yield of 37%, conversion of 40%, and selectivity of 92% EXAMPLE IV In still another run, technical-grade n-pentane, Vcontaining 22 p.p.rn. of Isulfur, and hydrogen, in va hydrogen/pentane mol ratio-of 1.5, were fed directly to the isomerization reactor using a freshly prepared catalyst of identical composition with the catalyst used in Examples I and II. It should be noted that naphthas containing 22 ppm. of

.sulfur are considered satisfactory feed stock for catalytic reforming, at temperatures of 850-1000 F. This isomerzation reaction was carried out at a pressure of 500 p.s.i.g., a temperature of 720 F., and `a liquid volume .hourly space velocity of 3.0. The initial product from the reactor in this run contained 33.6% isopentane, corresponding to a yield of 32.4% and selectivity of 95%. This run was continued for a period of 24 hours during which time the yield of isopentane decreased at a constantrateof about 0.7 unit per hour.

'EXAM PLE V In another run, technical-grade n-pentane having a sulfur content vof 22 Vppm. was -hydrodesulfurized, caustic-Washed, Water-washed, and dried -to reduce the sulfur Vcontent to 2-5 ppm. This feed, however, was not passed through the second desulfurizer unit to remove the remaining sulfur as in Examples -I to III. The partially desulfurized n-pentane feed was introduced directly into the catalytic isome-rization reactor at a temperature of 700 F., pressure of y500 p;s.1i.g., and a liquid volume hourly space velocity of 3.0, together With hydrogen in a hydrogen/pent-ane mol ratio of 1.0. The

`product from the reactor initially represented an isopen- EXAMPLE VI Technical-grade n-pentane 'was Vcatalyticallyand chemically desulfurized to 'a sulfur content less than L1 p.p.'m. as in Examplesl .to III. The desulfurized `n-pentane assises and hydrogen in a hydro-gen/n-pentane mol ratio of 2.2 were introduced into the catalytic isomerization reactor. In this run the catalyst used was 0.4% palladium metal on a 87-13 silica-alumina support. The reaction was carried out :at a temperature of 775 F., a pressure of 600 p.s.i.g., and -a liquid volume hourly space velocity of 3.5. The product from the reactor contained about 55% isopentane,.representing a yield of 55% and selectivity of 98%; This run was continued for a period of more than 400 hours during which time the yield of isopentane remained constant.

EXAMPLE VII In another run the following data were obtained which show the effect of sulfur` in the feed for the isomerization of n-pentane over a palladium-silica-alurnina catalyst. Technical grade n-pentane containing 20 p.p.m. sulfur was fed to the isomerization reactor. The catalystcontained 0.4% Pd on a 75/25 silica-alumina support. The operating conditions were as follows: pressure, 700 p.s.i.g., hydrogen/pentane mol ratio, 2.0; LVHSV, 2.0; and temperature, 725 F.. The variation of yield with time on stream is shown in Table I below:

Table I Time on Stream, hr. i-Cs, tivity,

percent percent EXAMPLE VIII In still another run the following data were obtained which show the effect `of sulfur in the feed for pentane isomerization, and the recovery of the catalytic activity when the feed is void of sulfur. The catalyst contained 0.6% Pd on 75/25 silica-alumina support. The operating conditions were as follows: pressure, 700 p.s.i.g.; hydrogen/pentane mol ratio, 2.0; LVHSV, 2.0; and temperature 700 F. The variation -of yield with time on stream land the recovery of catalyst lactivity with -a pure feed are shown in Table II below:

In `addition to the foregoing examples a number of experiments were run and the results graphically illustrated in Fig. 2. This graph shows the effect of sulfur in the hydrocarbon feed on the steady-state activity of a palladium catalyst. The reaction rate constants (K) in the various experiments were calculated by t-he equation:

K: @avec 1n where xzfractional yield, xezequilibrium yield. The relative activity ratio was determined as the ratio of isomerization reaction rate when sulfur is present in the hydrocarbon feed divided by the initial reaction rate. This therefore provides a measure of relative activity which is independent of test levels of yield and space velocity. As is apparent from the `graph the decline in activity attributable to trace amounts of sulfur is very great.

It is to be further noted that the catalyst poisoning by trace amounts of sulfur is similar for isomerization of C4-C7 n-paraflins other than n-pentane. When this process is carried out using n-paraflins of the C4-C7 range or mixtures thereof or naphtha cuts containing a large proportion of CFC, n-paraffns it is necessary for a practical process to maintain a sulfur concentration of less lthan l p.p.m.

From the foregoing examples, it is seen that the isomerization of low-molecular-Weight normal parain hydrocarbons using nickel, nickel-molybdena, or palladium metal catalysts supported on an acidic silica-alumina (S0-90% silica) support is unique in its extreme sensitivity to the presence of sulfur in the hydrocarbon feed. Metal catalysts when used for reforming of hydrocarbons at temperatures of 900 F. and above will tolerate sulfur in the hydrocarbon feed to the extent of 20 ppm. and more. Low-temperature isomerization with anhydrous aluminum chloride catalysts will similarly tolerate large amounts of sulfur in the hydrocarbon feed (see U.S. Patents 2,389,659 and 2,389,660). However, when the lrydroisomerization of C4-Cq paraiiins is attempted using a nickel, nickel-molybdena, or palladium catalyst supported on an acidic silica-alumina support, at temperatures of 650-800 F., the presence of even trace amounts of sulfur in the hydrocarbon feed is objectionable. In the case of base metal catalysts containing nickel, molybdenum, etc., the presence of any measurable amount of sulfur in the hydrocarbon feed results in the permanent loss of catalyst activity. The catalyst activity cannot be regained by subsequently reducing the sulfur content of the feed to zero. Furthermore, the sulfur-poisoned catalyst cannot be elfectively reactivated by the usual oxidation-reduction technique.

When noble metal catalysts such as palladium are used the effect of sulfur in the feed is very different. 4The catalyst activity diminishes with increasing amounts of sulfur. For any given sulfur concentration, the catalyst activity will diminish rapidly with time to a steady-state level at which it will remain indefinitely, so long as the sulfur content is constant. Since these catalysts are hydrogenation catalysts, the same weight of sulfur (as H28) leaves the reactor as that which enters as organic sulfur-containing compounds. Thereafter, when the sulfur content of the feed is reduced to zero, the catalyst regains its initial activity in -a few hours. It is therefore apparent that a sulfur content in the hydrocarbon feed of practically Zero (less than l ppm.) must be maintained if undue loss in catalyst activity is to be avoided.

While I have described my invention fully and cornpletely as required by the patent statutes, I wish it to be understood that within the scope of the appended claims this -invention may be practiced otherwise than as specifically described.

What is claimed is:

l. A hydroisomeriza-tion process which comprises treating a feed stock consisting essentially of at least one normal parain hydrocarbon in the C4-C7 range having a sulfur content in excess of l ppm. to reduce the sulfur content to a value less than about 1 p.p.m., contacting -a mixture of the desulfurizedl feed stock and hydrogen ywith a catalyst selected from the group consisting of nickel, nickel-molybdenum, and palladium, supported on an acidic silica-alumina support containing 50-90% silica, at a temperature of 650'800 F., pressure of -l000 psig., and hydrogen/hydrocarbon mol ratio of 0.5-5.0.

2. A process in accordance with claim l in Which the catalyst consists of nickel supported on a silica-alumina support containing 75-85% silica.

3. A process in accordance with claim l in which the catalyst consists of reduced nickel molybdate supported on a silica-alumina support containing 75-87% silica.

4. A process in accordance with claim l in which` the catalyst consists of palladium supported `on `a silicaalu support containing 75-87% silica.

l V5. A .process in accordance with claim 1 in which a sulfur-containing hydrocarbon feed is hydrodesu'lfurized and .freed of hydrogen sulde to vreduce the sulfur conftent to less `than 0.001% and klchen further desulfurized to produce a feed having .a sulfur content substantially less than 1 ppm.

6. A process in `accordance with claim 5 in which 7. A process in accordance with claim 6 in which the 15 isomerization catalyst consists of nickel supported on a siliczualumina support containing 75*87% silica.

vthe further desulfu-r-ization is carried out by contacting ,10

8. A process in accordance with claim 6 in which the isomerization catalyst consists of reduced nickel molybdate supported on a silica-alumina `support containing 75-87% silica.

9. A processinaccordance with claim 6 in which lthe .isomerization catalyst consists of palladium supported on a silica-alumina support containing 75-87% silica.

ReferencesCited in the ile of this patent UNITED STATES PATENTS 2,376,086 Reid lMay 15, 1945 2,718,535 McKinley et al. Sept. 20, 1955 2,769,760 Annable et al. Nov. 6, 1956 FOREIGN PATENTS 487,392 Canada Oct. 21, 1952 

1. A HYDROISOMERIZATION PROCESS WHICH COMPRISES TREATING A FEED STOCK CONSISTING ESSENTIALLY OF AT LEAST ONE NORMAL PARAFFIN HYDROCARBON IN THE C4-C7 RANGE HAVING A SULFUR CONTENT IN EXCESS OF 1 P.P.M. TO REDUCE THE SULFUR CONTENT TO A VALUE LESS THAN ABOUT 1 P.P.M., CONTACTING A MIXTURE OF THE DESULFURIZED FEED STOCK AND HYDROGEN WITH A CATALYST SELECTED FROM THE GROUP CONSISTING OF NICKEL, NICKEL-MOLYBDENUM, AND PALLADIUM, SUPPORTED ON AN ACIDIC SILICA-ALUMINA SUPPORT CONTAINING 50-90% SILICA, AT A TEMPERATURE OF 650*-800*F., PRESSURE OF 100-1000 P.S.I.G., AND HYDROGEN/HYDROCARBON MOL RATIO OF 0.5-5.0 